Disazo dyestuffs and complex heavy metal compounds thereof



United States Patent DISAZO DYESTUFFS AND CONHLEX HEAVY METAL COMPOUNDSTHEREOF Hans Ackermann, Riehen, near Basel, and Guido Schetty, Basel,Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swissfirm No Drawing. Application September 2, 1954, Serial No. 453,946

Claims priority, application Switzerland September 18, 1953 7 Claims.(Cl. 260-147) The present invention concerns the production of a newclass of metallisable disazo dyestuffs and the complex heavy metalcompounds thereof. It also concerns a process for the dyeing of laquersor of protein substances such as leather or hairs, chiefly however, forthe dyeing of natural or synthetic polypeptide fibres such as R2 4 (I)with an azo component usual in azo dyestuffs coupling in theneighbouring position to a hydroxyl group. In this Formula 1: A1represents a component usual in azo dyestufis which contains a hydroxylgroup in the neighbour ing position to the azo linkage, B1 and B2represent radi cals of the benzene series containing the azo linkage inthe o-position to the bridging member of both rings, and R1 to R4represent hydrogen, alkyl groups or constituents of organic ringsystems. All aromatic rings can contain the further substituents usualin azo dyestuffs, that is, for example, halogen, alkyl, alkoxy, nitr'o,acylamino, carboxyl, sulphonic acid, sulphonic acid amide groups,sulphonic acid amide groups organically substituted at the nitrogenatom, alkyl, aralkyl or arylsulphonyl groups.

Of the technical possibilities of producing the diazonium compoundsaccording to this invention, only a few are taken and more closelydescribed in the follow- 2,780,618 Patented Feb. 5, 1957 group issaponified, then on reacting a further molecule of an aromatico-nitrosulphonic acid halide compound, an a-o-nitrophenylsulphonyl-amidop-o-aminophenyl sulphonyl amidoalkane or cycloalkane isproduced. For example, u-o-nitrobenzene sulphonyl-pro-aminobenzenesulphonyl ethylene diamine can be produced according to this method.These nitro-amino compounds can either be diazotised and coupled with anazo component coupling in the neighbouring position to a hydroxyl groupand then the nitro group reduced to the amino group and the latterdiazotised or these nitro-amino compounds can first be acetylated andthe nitro group reduced to the amino group, diazotised, coupled with anazo component coupling in a neighbouring position to a hydroxyl groupand the acetylamino group saponified and then diazotised.v

In this way, diazo compounds of the general Formula I arepbtained whichare particularly well suited for the production of unsymmetrical disazodyestuffs.

(b) Also a.fl-diarninoalkanes or cycloalkanes or ophenylene diamines canbe diacylated with 2 mols of an o-nitrophenyl sulphonic acid halide, thenitro groups reduced to amino groups and tetrazotised, and then thereaction is performed in steps beginning with the'coupling of one mol ofan azo component coupling in the neighbouring position to a hydroxylgroup. In this manner diazo compounds of the general Formula I are alsoobtained.

The last method described above is suitable particularly for theproduction of symmetrical disazo dyestuflfs according to the presentinvention. Naturally, the reaction need not be performed in steps.

In the process according to the present invention, azo components usualin azo dyestufis which couple in the neighbouring position to a hydroxylgroup are the known compounds which couple in the neighbouring positionto.

sulphonic acid amide groups organically substituted atthe nitrogen atom,or alkyl sulphonyl groups.

The disazo dyestufis according to the present invention obtainedaccording to the processes described, correspond to the general FormulaII:

. 1'1. i. an wherein the symbols A1, B1, B2, R1-R4 have the meaningsgiven in Formula I and A2 represents an azo component coupled in theneghbouring position to an enolic or phenolic hydroxyl group.

In the process according to the present invention the components are sochosen with regard to the intended use that the disazo dyestufifis orthe complex heavy metal compounds thereof are of a suitable solubility.In heavy metal containing disazo dyestuffs which are soluble inlacquers, it is of advantage, for example, to avoid the presence of acidwater solubilising groups, such as, e. g. sulphonic acid or carboxylicacid groups. For the production of heavymetal containing disazodyestulis whicli draw on to keratine fibres from a neutral to weaklyacid medium the components are also so chosen that no acid watersolubilising groups are present but care is taken that the end productcontains substituents having a favourable effect on the watersolubility.

As such, sulphonic acid amide groups, sulphonic acid amide groupsorganically substituted at the nitrogen atom, low molecularalkylsulphonyl and acylamino groups can be used. To produce disazodyestuffs according to the present invention, if desired containingheavy metal, which dyestuffs draw from an acid bath, the components areso chosen that the end products contain at least one sulphonic acidgroup.

The disazo dyestuffs according to the present invention can bemetallised by methods known, per so either on the fibre oradvantageously, in substance. Preferably the inorganic, organic orcomplex salts of trivalent chromium asv well as those of. cobalt canbeused as agents yielding heavy metal. The metallisation can be performedin aqueous or. organic solution or suspension, e. g. in the presence oflower. alcohols, hydroxyalkyl ethers, ethers forming a ring such asdioxanes, carboxylic acid amides such as dimethyl formamide oracetamide. It may be performed either open or under pressure at a raisedtemperature. The avoidance of a strongly mineral acid reaction in themetallising agent is advantageous. The agents yielding heavy metal areused with advantage in. such amounts that there is at least one heavymetal atom to a dyestuif'molecule.

The disazo dyestuffs according to the present invention are obtained inthe form of yellow, brown or darkpowders according to the compositionand, on keratine material, they produce yellow, yellow-brown, brown-red,

brown, violet-brown to olive heavy metal dyeings which are distinguishedparticularly by good fastness to light.

The following examples illustrate the invention without limiting it inany way. Where not otherwise stated, the parts are given as parts byweight and the temperatures are in degrees centigrade. The relationshipof parts by weight to parts by volume is as that of kilogrammes tolitres.

EXAMPLE 1 37 parts of bis-(2-aminobenzene sulphonic acid)-ethylenediamide are dissolved hot in 400' parts of glacial acetic acid and 58parts of concentrated hydrochloric acid are added. 14 parts of sodiumnitrite, as a cone centrated solution, are added dropwise at l520 andthe whole is left to diazotise completely for 1 hour. The tetrazoniumsolution is mixed with a solution of 29.7 parts of fi-naphthol in 100parts of glacial acetic acid and 56 parts of sodium acetate are addedwhile stirring. The dyestuif, which corresponds to the formulaprecipitates in the form of scarlet red crystals which can be drawn offunder suction and washed. The disazo dyestuff is pasted in 750 parts ofethylene glycol and concentrated caustic soda lye is added until acomplete solution is obtained and a sample diluted with water has. aweakly alkaline reaction to mimosa paper. 32parts of chromic acetate(corresponding to 9.1 parts of CrsOs) are added and the whole is. heatedwhile stirring, at 120-130 until the original dyestuff has disappeared;The red-brown solution is poured onto a sodium chloride solution and thechromium containing dyestuif which agvsogere precipitates is filteredoff. It is abrown powder which dissolves well in hot water and dyes woolfrom a weakly acid bath in red-brown shades which have excellentfastness to light. The solution in nitrocellulose lacquer is alsored-brown.

A similar dyestuff is obtained if instead of 37 parts ofbis-(Z-aminobenzene sulphonic acid)-ethylene diamide, 39.8 parts ofbis-(Z-aminobenzene sulphonic acid)-a.;8- dimethyl ethylene diamide,38.4 parts of bis-(Z-aminobenzene-sulphonic acid)- x-methyl ethylenediamide or 39.8 parts of bis-(2-aminobenzene sulphonicaCid)-oc.ocdimethyl ethylene diamide are used.

EXAMPLE 2 43.9 partsof bis-(2-amino-4mhlorobenzene sulphonicacid)-ethylenediamide are tetrazotised as described in Example. 1, mixedwitha solution of, 47 parts of Z-naphthol-6-sulpl1onic acid in parts ofglacial acetic acid and the whole is addedto, 5.6, parts of" sodiumacetate. On completion of the coupling, the dyestuii is precipitated bydiluting with water. The dyestufi is dissolved in 750 parts of waterwith caustic soda lye to give an alkaline reaction to mimosa paper, 260parts by volume of a solution of ammonium chromosalicylate,corresponding to 9.2 parts of CrzOs are added, and the whole is boiledunder reflux for 10 hours. The complex chromium compound is precipitatedby the addition of sodium chloride. It is a brown powder which dyes woolfrom a sulphuric acid bath in fast to light red-brown shades.

A similar dyestuff is obtained if instead of 43.9 parts ofbis-(Z-aminoA-chlorobenzene sulphonic acid)-ethylene diamide, 39.8 partsof bis-(2-aminobenzene sulphonic acid) -a.fi-dimetliyl ethylene diamide,38.4 parts of bis-(2eaminobenzene sulphonic acid)-a-methyl ethylenediamide, 39.8 parts of bis-.(2-aminobenzene sulphonic acid)-a.a-dimethylethylene diamide, 41.8 parts of bis- (2-aminobenzene sulphonicacid)-o-phenylene diamide or 41.2 parts of 1.2-bis-(2'-aminobenzenesulphamido)-cyclohexane areused.

EXAMPLE. 3

The non-metal containing disazo dyestuif obtained according to Example 1in 250 parts of acetamide is warmed to l30-l40 with 30 parts of cobaltacetate (corresponding to 7.1 parts of cobalt) until. all the originaldyestutf has disappeared; The reaction mixture is poured on to sodiumchloride solution and the precipitated dyestuff is filtered ofi. Itdyeswool from a weakly acid bath in olive greenshades:

EXAMPLE 4 40.5 parts of a-.(2-aminobenzene sulphonic acid)-fl-(2-amino-4-chlorobenzene sulphonic acid)-ethylene diamide aretetrazotised as described in Example 1 and, a

solution of- 36.6 partsof. 1-pheny1-3-methyl-5-pyrazolone.

in 100 parts of glacial acetic acid is added. The excess hydrochloric,acid isneutralised with 56 parts of sodium acetate and on completion ofthe coupling, the yellow dyestufi' is filtered off. The well washeddisazo dyestufif is pasted in 750. parts of. ethylene glycol, 12 partsof sodium hydroxide. and 32 parts of. chromic acetate (corresponding. to9.1 parts'of CrzOa) are added and the Whole is. heated at -135 whilestirring until the metallisation process is complete. The yellowsolution is poured into a sodium chloride solution and the precipitateddyestufi is filtered oil. It is a yellow powder whichdyes wool from aweakly acid bath in greenishyellow shades which have very good fastnessto light.

EXAMPLE 5 41.8 parts of bis-(2-aminobenzene sulphonic acid)-ophenylenediamide are tetrazotised" according to Example 1 and a solution of'30.2parts of B-naphthol in'200 parts of glacial acetic acid is added. 47parts of sodium acetate are added whereupon the coupling proceeds veryquickly. The reaction mixture is stirred for 1 hour at room temperature,the disazo dyestuif is filtered OE and thoroughly washed with hot water.The dried dyestulf is pasted in 200 parts of ethylene glycol, 32 partsof chromic acetate (corresponding to 9.1 parts of CrzOs) and 13.6 partsof sodium hydroxide are added and the whole is heated for 1 hour at130l35 while stirring. The chroming mixture is then poured into dilutedsodium chloride solution and the brown chromium complex is filtered off.It dyes wool from a weakly acid bath in brown shades which are fast tolight.

EXAMPLE 6 44.7 parts of the compound of the formula:

NH-COCH; HzN- 01 monoazo dyestuif is filtered off. It is thoroughlywashed with water, dissolved in 500 parts of water with 25 parts ofsodium hydroxide and the whole is boiled for 8 hours under reflux. Aftercooling, 7 parts of sodium nitrite are added and at 15-20 105 parts ofconcentrated hydro- 55 chloric acid are quickly added. The mixture isleft to diazotise completely for two hours, the diazonium compound isfiltered otf, poured into a solution of 15.1 parts of B-naphthol in 250parts of glacial acetic acid and then 20 parts of sodium acetate areadded. The disazo dyestuff precipitates in the form of orange colouredcrystals. It is filtered olf, and washed with water. The dried dyestutfis pasted in 500 parts of ethylene glycol, 32 parts of chromic acetate(corresponding to 9.1 parts of CrzOa) are added and the mixture isheated at 125-135 until the metallisation process is complete, duringwhich the reaction is kept alkaline to phenolphthalein by the additionof caustic soda lye. The chroming mixture is poured into sodium chloridesolution and the precipitated dyestulf is filtered off. It is a brownpowder which dyes wool from a Weakly acid bath in orange-brown shadeswhich have excellent fastness to light.

The following dyestuifs and the metal containing compounds thereof canbe produced according to the information given in the above examples:

S OINH! No. Tetrazo component Shade Azo component Metal 1hls-(2-aminobenzene tert. p-amyl phenyl. Or yellowish sulphomc acid)-brown. ethylene diemide. 2 -do 3.4-dimethyl phenol. Or Do.5.8-dichloro-1-naph- Cr violet thol. brown. carbomethoxyami- Cr Do.

no-naphthol-IJ. 1-(3'-ch orophenyD- 0r greenish a-methyl-fi-pyrazyellow.

clone. 6.. bis-(2-amino-4- 1-(3-sul hamido- Or D chloro-b enzenephenyl-3-methylsulphonic acid)- 5-pyrazolone. ethylene diamide.

7 do B-na hthol Or red-brown.

8 9 0 Co olive green 9 1.2-b1s-(2'-ammo- -do Cr red-brown.

benzene-Sui hamido)-cye1oexane.

10..-- d0 1-(2-toly1'5-methyl- Or greenish suIphonyD3-methyellow.yl-5-pyrazo1one.

11 bis-(z-aminobenzene A =2.6-na hthol Cr orangesulphoulc acld)- sulhami e; Aa= brown. ethylene dlamide. l-p enyl-B-methyl-5-pyrazolone.

12. bis-(2-am1no-5-nitro- B-naphthol Or brown.

benzenesulphonie acidl-ethylene diamidered-brown.

13.. bis-(2-amino-4- zfi-naghthol, sulph- Or chino-benzene am e.

sulphonic acid)- ethylene diamide. 14..-- bis-(2-em1nobenzene A1 2.fi-uaph th 01 Or Do.

sulphonic acid)- sulphonic acid; ethylene diamide. Az=fl-naphthol.

Following are formulae of the unmetallized dyestuffs corresponding torepresentative products obtained according to the foregoing table:

No. 5 I

N=N--cH'--o--om 0H s OrNH-CHr-CHi-N'H-S Or OH What we claim is:

wherein A1 and A2 represent the radical of a member 75 selected from thegroup consisting of phenolic, naphtholic and enolic coupling components,containing the hydroxyl 4. The complex chromium compound of the disazogroup in the ortho-po'sition to the 2120 group, X1 and X2 dyestufihaving the formula:

H2O|O(|JHN=N N=N(?H(RCH2 o 00 N/ OPNHGO H2-CH:NHS O2 \N each represents'a member selected from the group con- 5. The complex chromium compoundof the disazo sisting of H, Cl and N02, R1, R2, R3 and R4 represent adyestutf having the formula:

HaC (HJ(|JH=N=N N=NCH-C]CH N 00 00 N \N/ -SOzNH-GH2CH2NHSO2 Cl- I-so,NH1 HQNSOZQ member selected from the group consisting of hydrogen 6.The complex chromium compound of the disazo and alkyl radicals which maybe joined together to form dye'stutf having the formula: part of asix-membered isoeyclic ring system, and the complex chromium and cobaltcompounds of said dyestutfs.

2. The complex chromium compound of a disazo dyestuff having the generalformula: I

AN N N=N-A 1?: Ba I SOr-NH-CHrCHr-NH-SOr OH sor nn-c c-nn-sor C1 i X X7. The complex chromium compound of the disazo wherein A represents theradical of a member selected dyestuff having the formula: from the groupconsistin'g'of 'napht holic' and 'pyra'zol'onic coupling componentscontaining the hydroxyl group in SOZNH, 302N112 the ortho position tothe azo group, X represents a mem- 40 t ber selected from the groupconsisting of H, Cl and N02, R1, R2, R3 and R4 represent a memberselected from the group consisting of hydrogen and alkyl radicals whichmay be joined together to form part of a six-membered isocyclic ringsystem, A being free from carboxylic acid OH OH and sulphoni'c acidgroups.

3. The complex chromium compound of the disazo O1 dyestuffhaving theformula:

References Cited in the file of this patent UNITED STATES PATENTS I 2133787 Northey Oct 18 1938 H N p H CE'UHTNH OH 2,1 4,735 Rossande'r .-July4, 1939 2,438,754 'Krc'bser et a1. Mar. 30, 1948 2,448,853 Allen 'et a1.Sept. 7, 1948

1. A DYESTUFF SELECTED FROM THE CLASS CONSISTING OF THE DISAZO DYESTUFFSHAVING THE GENERAL FORMUL A: